UV-Light-Induced Morphological Transformation of Spiropyran Assemblies from Irregular Sheet-like Structures to Nanospheres.

Studies on self-assembling systems with a controllable morphology responding to light stimulation are significant for revealing the process and mechanism of assembly. Here, a molecule of spiropyran derivative (SP) possessing photoresponsive assembly morphology is constructed. SP self-assembles into irregular sheet-like structures whose morphology can be significantly transformed into regular nanospheres under continuous ultraviolet light stimulation. The UV-vis absorption spectra indicate that 56% of SP are isomerized from closed-ring form (SPC) to open-ring form (SPO) with color changes from colorless to magenta. Furthermore, theoretical calculations demonstrate that SPO-SPO aggregates possess stronger van der Waals forces than do SPC-SPC aggregates and tend to form stable intermediates combined with SPO isomers. Therefore, the isomerization of SP from SPC to SPO and the differences in intermolecular interactions are important factors in the morphological transition. Our study provides an efficient strategy to modulate the assembled morphology, which holds great promise to be applied in the field of smart materials.

Light-Modulated Morphological Transformation of Spiropyran Derivative from Nanosphere to Nanorod.

The construction of tunable morphological systems has important implications for understanding the mechanism of molecular self-assembly. In this study, a spiropyran derivative M1 is reported with light-responsive assembly morphology, which can be tuned from nanosphere to nanorod by ultraviolet light irradiation. The absorption spectra show that M1 molecules are transformed from closed-ring (SP) isomers into open-ring (MC) isomers and start to form H-aggregates with increasing irradiation time. Density functional theory calculations indicate that MC-MC isomers possess stronger binding energy than SP-SP isomers. The MC isomers may thus facilitate the dissociation of the SP-SP aggregates and promote the change of self-assembled morphology with the aid of stronger π-π stackings and dipole-dipole interactions. The research gives an effective method for modulating the morphology of assemblies, with great potential for applications in smart materials.

Reconstruction of Solid Electrolyte Interphase with SrI2 Reactivates Dead Li for Durable Anode-Free Li-Metal Batteries.

Without excess Li, anode-free Li-metal batteries (AFLMBs) have been proposed as the most likely solution to realizing highly-safe and cost-effective Li-metal batteries. Nevertheless, short cyclic life puzzles conventional AFLMBs due to anodic dead Li accumulation with a local current concentration induced by irreversible electrolyte depletion, insufficient active Li reservoir and slow Li+ transfer at the solid electrolyte interphase (SEI). Herein, SrI2 is introduced into carbon paper (CP) current collector to effectively suppress dead Li through synergistic mechanisms including reversible I- /I3 - redox reaction to reactivate dead Li, dielectric SEI surface with SrF2 and LiF to prevent electrolyte decomposition and highly ionic conductive (3.488 mS cm-1 ) inner layer of SEI with abundant LiI to enable efficient Li+ transfer inside. With the SrI2 -modified current collector, the NCM532/CP cell delivers unprecedented cyclic performances with a capacity of 129.2 mAh g-1 after 200 cycles.

Electrolyte Engineering for High-Voltage Lithium Metal Batteries.

High-voltage lithium metal batteries (HVLMBs) have been arguably regarded as the most prospective solution to ultrahigh-density energy storage devices beyond the reach of current technologies. Electrolyte, the only component inside the HVLMBs in contact with both aggressive cathode and Li anode, is expected to maintain stable electrode/electrolyte interfaces (EEIs) and facilitate reversible Li+ transference. Unfortunately, traditional electrolytes with narrow electrochemical windows fail to compromise the catalysis of high-voltage cathodes and infamous reactivity of the Li metal anode, which serves as a major contributor to detrimental electrochemical performance fading and thus impedes their practical applications. Developing stable electrolytes is vital for the further development of HVLMBs. However, optimization principles, design strategies, and future perspectives for the electrolytes of the HVLMBs have not been summarized in detail. This review first gives a systematical overview of recent progress in the improvement of traditional electrolytes and the design of novel electrolytes for the HVLMBs. Different strategies of conventional electrolyte modification, including high concentration electrolytes and CEI and SEI formation with additives, are covered. Novel electrolytes including fluorinated, ionic-liquid, sulfone, nitrile, and solid-state electrolytes are also outlined. In addition, theoretical studies and advanced characterization methods based on the electrolytes of the HVLMBs are probed to study the internal mechanism for ultrahigh stability at an extreme potential. It also foresees future research directions and perspectives for further development of electrolytes in the HVLMBs.

Boosting the High Performance of BiFeO3-BaTiO3 Lead-Free Piezoelectric Ceramics: One-Step Preparation and Reaction Mechanisms.

One of the notorious problems in BiFeO3-based piezoelectric ceramics is how to limit the formation of Bi25FeO39 and Bi2Fe4O9 impurities to achieve excellent piezoelectric performance. In this study, a one-step preparation technology, namely, excluding PVA, calcining, and sintering are completed in one step, instead of three steps in the ordinary sintering method, is developed to prepare BiFeO3-xBaTiO3 (BF-xBT) ceramics. The significance of this one-step method is that the thermodynamically unstable region of BiFeO3 is successfully avoided based on the Gibbs free energy of BiFeO3, Bi25FeO39, and Bi2Fe4O9. Benefiting from preventing the formation of Bi25FeO39 and Bi2Fe4O9 impurities, the resultant ceramics show dense structures, macroscopic stripe domains, and a small number of island domains and display saturated P-E curves, sharp I-V characteristics, butterfly-shape S-E loops, and good piezoelectric properties (d33 = 174-199 pC/N; TC = 494-513 °C). By analyzing X-ray diffraction patterns of BF-xBT (0 ≤ x ≤ 1) powders at different calcination temperatures (Tcal), the different reaction mechanisms between 750 °C ≤ Tcal ≤ 900 °C and 950 °C ≤ Tcal ≤ 1000 °C are revealed. When 750 °C ≤ Tcal ≤ 900 °C, Bi3+ diffuses into Fe2O3 particles to form BiFeO3 and Bi25FeO39 and then reacts with BaTiO3; in this temperature range, the formed Bi25FeO39 is hard to eliminate. At 950 °C ≤ Tcal ≤ 1000 °C, Bi3+ and Fe ions simultaneously diffuse into BaTiO3 to form BF-xBT, which is beneficial to preventing the formation of Bi25FeO39 and the improvement of performance.

A Single-Layer Composite Separator with 3D-Reinforced Microstructure for Practical High-Temperature Lithium Ion Batteries.

Incorporation of ceramic materials into separators has been frequently applied in both research and industry to improve the overall high-temperature performances of lithium ion batteries. However, inorganic ceramic particles tend to form aggregation in separators and even fall off in the separator matrix due to the inferior combination between ceramic particles and polymer matrix, giving rise to a decrease in separator porosity and thus the degradation of battery performances. Herein, a single-layer core-shell architecture is designed to reinforce the polymer matrix through encircling Al2 O3 particles by poly(vinylidene fluoride) with strong inter-molecular interaction. The 3D-reinforced microstructure effectively improves pore distribution and thermal stability to resist the dimensional deformation at high temperatures, thus giving rise to a high Coulombic efficiency of 99.16% and 87.5% capacity retention after 500 cycles at 80 °C for LiFePO4 /Li batteries. In particular, the excellent performances of the proposed separator microstructure are confirmed with a thickness value of commercial separators. This work provides a promising strategy to fabricate a core-shell structural composite separator for stable lithium ion batteries at high temperatures.

TGF-ß1-overexpressing mesenchymal stem cells reciprocally regulate Th17/Treg cells by regulating the expression of IFN-γ.

Transforming growth factor (TGF)-ß1 and mesenchymal stromal cells (MSCs) are two effective immunosuppressive agents for organ transplantation technology. This study aims to explore the molecular mechanism of TGF-ß1-overexpressed MSCs on T cell immunosuppression. To achieve that, BM-MSCs were isolated from canine bone marrow, and their osteogenic differentiation and surface markers were detected. The TGF-ß1 gene was transferred into lentivirus and modified MSCs (TGF-ß1/MSCs) by lentivirus transfection. Furthermore, TGF-ß1/MSCs were co-cultured with T cells to investigate their effect on differentiation and immune regulation. Results showed that TGF-ß1/MSCs significantly downregulated the proportion of CD4+ CD8+ T cells in lymphocytes and significantly upregulated the proportion of CD4+ CD25+ T cells. Moreover, TGF-ß1/MSCs significantly upregulated the expression of IL-10 in CD4+ T cells and downregulated the expression of IL-17A, IL-21, and IL-22. Meanwhile, interferon-γ (IFN-γ) neutralizing antibody blocked the effects of TGF-ß1/MSCs on the differentiation inhibition of Th17. Overall, our results confirm the strong immunosuppressive effect of TGF-ß1/MSCs in vitro and demonstrate that IFN-γ mediates the immunosuppressive effect of TGF-ß1/MSC.

A Novel Extreme Learning Machine Classification Model for e-Nose Application Based on the Multiple Kernel Approach.

A novel classification model, named the quantum-behaved particle swarm optimization (QPSO)-based weighted multiple kernel extreme learning machine (QWMK-ELM), is proposed in this paper. Experimental validation is carried out with two different electronic nose (e-nose) datasets. Being different from the existing multiple kernel extreme learning machine (MK-ELM) algorithms, the combination coefficients of base kernels are regarded as external parameters of single-hidden layer feedforward neural networks (SLFNs). The combination coefficients of base kernels, the model parameters of each base kernel, and the regularization parameter are optimized by QPSO simultaneously before implementing the kernel extreme learning machine (KELM) with the composite kernel function. Four types of common single kernel functions (Gaussian kernel, polynomial kernel, sigmoid kernel, and wavelet kernel) are utilized to constitute different composite kernel functions. Moreover, the method is also compared with other existing classification methods: extreme learning machine (ELM), kernel extreme learning machine (KELM), k-nearest neighbors (KNN), support vector machine (SVM), multi-layer perceptron (MLP), radical basis function neural network (RBFNN), and probabilistic neural network (PNN). The results have demonstrated that the proposed QWMK-ELM outperforms the aforementioned methods, not only in precision, but also in efficiency for gas classification.

Cytotoxic and apoptotic effects of constituents from Millettia pachycarpa Benth.

The aim of this study is to investigate the cytotoxic and apoptotic effects of constituents from the seeds of Millettia pachycarpa Benth. Fourteen compounds (1-14) including one novel chalcone (10) were isolated as active principles from Chinese herbal medicine M. pachycarpa Benth. Their structures were identified by using spectroscopic methods. All isolates were then evaluated for their cytotoxic effects against several cancer cell lines (HepG2, C26, LL2 and B16) with cisplatin as a positive control. And their apoptosis-inducing effects were tested against HeLa-C3 cells with taxol as a positive control. Both studies showed that compounds 1, 2, 7 and 10 demonstrated significant cytotoxic and apoptotic effects against cancer cells. Moreover, in the apoptosis assay the novel chalcone (10) showed strong apoptosis inducing effects at a concentration of 2µM within 36h. It was found to be the most potent apoptotic inducer of the compounds isolated from M. pachycarpa Benth.

Application of step-wise gradient high-performance counter-current chromatography for rapid preparative separation and purification of diterpene components from Pseudolarix kaempferi Gordon.

In general, simultaneously separation and purification of components with a broad polarity range from traditional Chinese medicine (TCM) is a challenge by an ordinary high-speed counter-current chromatography (HSCCC) method. In this paper, we describes a rapid and efficient separation method of combining three-step gradient elution and two-step flow-rate gradient elution using high-performance counter-current chromatography (HPCCC) to separate 8 diterpene compounds simultaneously within 80 min in a single run from the alcohol extract of Pseudolarix kaempferi Gordon. This separation process produced 166 mg pseudolaric acid B O-ß-d-glucopyranoside (PABGly), 152 mg pseudolaric acid C (PAC), 8 mg deacetylpseudolaric acid A (deacetylPAA), 5 mg pseudolaric acid A O-ß-d-glucopyranoside (PAAGly), 484 mg pseudolaric acid B (PAB), 33 mg pseudolaric acid B methyl ester (PAB methyl ester), 10mg pseudolaric acid A (PAA) and 18 mg pseudolaric acid H (PAH) from 1.0 g crude sample with purities of 98.6%, 99.6%, 92.3%, 92.2%, 99.2%, 99.4%, 98.3%, 91.0%, respectively. Our study indicates that the suitable combination of step-wise gradient elution and flow-rate gradient elution using HPCCC is an effective strategy to separate complex components from natural products.

Separation of anthraquinone compounds from the seed of Cassia obtusifolia L. using recycling counter-current chromatography.

Recycling counter-current chromatography (CCC) together with step-gradient CCC and medium-pressure liquid chromatography (MPLC) was employed to separate nine anthraquinone compounds from Cassia obtusifolia L. in this study. The results showed that recycling CCC is a powerful tool for compounds that are difficult to separate with common elution mode. CCC was the better option for crude material while MPLC had advantage for the final tuning. The combination of recycling CCC and MPLC could simplify the method exploring process in the separation process. The structures of these compounds were identified according to their mass spectra, by (1)H-NMR and compared with standard compounds.

Elution-extrusion counter-current chromatography separation of five bioactive compounds from Dendrobium chrysototxum Lindl.

The elution-extrusion counter-current chromatography (EECCC) method was firstly developed by Berthod in 2003 and has been used in natural products separation in recent years. The advantages of this method have been well documented such as reducing the separation time and solvent consumption. In the EECCC method, the time point of the extrusion step is very important during the whole separation process as it directly affects the resolutions, separation time and solvent consumption. However, how to choose a suitable time point to perform the extrusion step without decreasing the resolution has not been studied yet. In the present study, a strategy for systematically calculating the time point for extrusion was developed in theory and five bioactive compounds from the extract of Dendrobium chrysototxum Lindl. were separated and compared using normal CCC and EECCC method. Our results demonstrated that the accurate time point to perform the extrusion could be calculated and reduced both separation time and solvent consumption without losing separation performance. Using this EECCC method, five bioactive compounds were separated and purified with high purity. The separation time and solvent consumption were decreased from 200 min to 100 min and 5-2.5L during the separation process while the resolutions were still acceptable. Finally, 63 mg, 48 mg, 97 mg, 162 mg and 43 mg of hydroxyl phenanthrenes and bibenzyls with the purity of 98.7%, 98.0%, 98.2%, 99.0% and 98.7%, respectively were isolated from 1.2 g crude extract of D. chrysototxum Lindl. initially purified by column chromatography in one step separation. The purities of compounds were determined by HPLC. Their structures were identified by electrospray ionization-mass spectrometry (ESI-MS) and NMR.

Separation of honokiol and magnolol by intermittent counter-current extraction.

Recently, intermittent counter-current extraction (ICcE) has been developed and shown its advantage in improving resolution between targeted compounds. However, how to choose suitable parameters to increase the throughput has not been systematically studied yet. In present work, we first calculated theoretically the conditions to carry out ICcE elution mode. Then, honokiol and magnolol were separated as model compounds using ICcE elution mode to confirm our conclusion. After parameters like sample concentration and sample feed were optimized in analytical high-performance counter-current chromatography (HPCCC), the separation process was scaled up to preparative HPCCC successfully. 12.8 g honokiol and 16.1g magnolol were separated from 30 g mixture with purities of 98.6% and 93.7%. And the throughput of target isolation of ICcE elution mode was at least 3.75 x higher than isocratic elution mode with the same HPCCC instruments. Our results confirmed our theory calculation and demonstrated the enormous potential of ICcE on preparative separation of binary mixture.

Purification of honokiol derivatives from one-pot synthesis by high-performance counter-current chromatography.

This paper describes the application of high-performance counter-current chromatography (HPCCC) as a fast, useful and economic alternative for the separation and purification of seven honokiol derivatives (two of them are isomers), which were synthesized by a one-pot procedure. Five honokiol derivatives were successfully separated by n-hexane-ethyl acetate-methanol-water solvent system at three different volume ratios in a step-gradient elution. Two derivatives were obtained through a cycle elution mode. The whole separation process produced 366.3 mg, 323.6 mg, 242.8 mg, 216.2 mg, 203.5 mg, 185.8 mg and 279.3 mg of 3'-formylhonokiol (1), 2'-methoxy-3'-formylhonokiol (2), 2'-methoxyhonokiol (3), 4-methoxyhonokiol (4), 3',5-diformylhonokiol (5), 2',4-dimethoxy-3'-formylhonokiol (6) and 2',4-dimethoxyhonokiol (7) from crude sample of 3 g with purities of 98.7%, 99.3%, 98.6%, 98.2%, 99.0%, 98.4% and 99.2%, respectively. The purities and structural identification were determined by HPLC, (1)H NMR, (13)C NMR and mass spectroscopy.

Enrichment and isolation of barbigerone from Millettia pachycarpa Benth. using high-speed counter-current chromatography and preparative HPLC.

Enrichment of the anti-tumor compound barbigerone along with a rotenoid derivative from Millettia pachycarpa Benth. was performed by a two-step high-speed counter-current chromatography (HSCCC) separation process. In the first step, 155.8 mg of target fraction (Fra6) was obtained from 400 mg ethyl acetate extract of M. pachycarpa Benth. with an increase in barbigerone from 5.1 to 13% via HSCCC using a solvent system of n-hexane-ethyl acetate-methanol-water (5:4:5:3, v/v) under normal phase head to tail elution. HSCCC was repeated to eliminate the major contaminant in this initial fraction 6. After a separation time of 65 min, 22.1 mg barbigerone of 87.7% purity was obtained from Fra6 with the ternary solvent system of n-hexane-methanol-water (2:2:1, v/v) under normal phase elution. Finally, preparative HPLC was employed for the further isolation of barbigerone and the rotenoid derivative. The structures were confirmed by ESI-MS, (1)H NMR and (13)C NMR.

Thermochemical structures beneath Africa and the Pacific Ocean.

Large low-velocity seismic anomalies have been detected in the Earth's lower mantle beneath Africa and the Pacific Ocean that are not easily explained by temperature variations alone. The African anomaly has been interpreted to be a northwest-southeast-trending structure with a sharp-edged linear, ridge-like morphology. The Pacific anomaly, on the other hand, appears to be more rounded in shape. Mantle models with heterogeneous composition have related these structures to dense thermochemical piles or superplumes. It has not been shown, however, that such models can lead to thermochemical structures that satisfy the geometrical constraints, as inferred from seismological observations. Here we present numerical models of thermochemical convection in a three-dimensional spherical geometry using plate velocities inferred for the past 119 million years. We show that Earth's subduction history can lead to thermochemical structures similar in shape to the observed large, lower-mantle velocity anomalies. We find that subduction history tends to focus dense material into a ridge-like pile beneath Africa and a relatively more-rounded pile under the Pacific Ocean, consistent with seismic observations.